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H
D
7
Li
9
Be
10
B
11
B
12
C
13
C
14
N
15
N
16
O
17
O
19
F
23
Na
24
Mg
25
Mg
27
Al
28
Si
29
Si
31
P
32
S
33
S
35
Cl
37
Cl
2
% trong t
nhin
S
proton
99,98
1,56.102
92,57
100
18,83
81.17
98,89
1,108
99,635
0,365
99,96
3,7.10 -2
100
100
89,9
10,05
100
95,3
4,70
100
99,26
0,74
75,4
24,6
1
1
3
4
5
5
6
6
7
7
8
8
9
11
12
12
13
14
14
15
16
16
17
17
S
ntron
1
4
5
5
6
6
7
7
8
8
9
10
12
12
13
14
14
15
16
16
17
18
20
nhy
tng i *
1/2
1
3/2
3/2
3
3/2
0
1/2
1
1/2
0
5/2
1/2
3/2
0
5/2
5/2
0
1/2
1/2
0
3/2
3/2
3/2
2,793
0,857
3,256
1,177
1,801
2,688
1,000
9,64.103
0,294
1,39.102
1,99.102
0,165
Tn s
NMR
(MHz)**
100
15,4
38,8
14,0
10,7
32,2
0,702
0,404
0,283
1,59.102
1,01.103
1,04.103
25,1
7,2
10,1
1,893
2,627
2,216
2,91. 10 -2
0,834
9,27. 10 -2
13,5
94,0
26,5
0,855
3,639
2,68. 10 -2
0,207
6,1
26,0
0,555
1,131
7,85. 10 -2
6,64. 10 -2
19,9
40,5
0,643
0,821
0,683
2,26. 10 -3
4,71. 10 -3
2,72. 10 -3
7,67
9,79
8,15
49
ng
v
39
K
As
79
Br
81
Br
115
Sn
117
Sn
119
Sn
199
Hg
201
Hg
203
Tl
205
Tl
207
Pb
75
% trong t
nhin
S
proton
S
ntron
nhy
tng i *
93,08
100
50,57
49,43
0,35
7,67
8,68
16,86
13,24
29,52
70,48
21,11
19
33
35
35
50
50
50
80
80
81
81
82
20
42
44
46
65
67
69
119
121
122
124
125
3/2
3/2
3/2
3/2
1/2
1/2
1/2
1/2
3/2
1/2
1/2
1/2
0,391
1,435
2,099
2,263
0,913
0,995
1,041
0,499
0,607
1,596
1,611
0,584
5,08. 10 -4
2,51. 10 -2
7,86. 10 -2
9,84. 10 -2
3,50. 10 -2
4,53. 10 -2
5,18. 10 -2
5,72. 10 -3
1,90. 10 -3
0,187
0,192
9,13. 10 -3
Tn s
NMR
(MHz)**
4,67
17,1
25,1
27,0
31,1
37,0
37,6
17,9
7,24
57,0
57,7
20,9
qung.
Spin ht nhn c to thnh v phng din vect l s cng ca thnh phn ht
h = hng s Planck
I = s lng t spin ht nhn
i vi cc ng v ht nhn khc nhau I c th bng 0, 1/2, 1, 3/2, ..., 7.
Khi s th t (s proton) v khi lng (s proton + neutron) ca mt ht nhn u
(2)
k = pk
= t l hi chuyn t ca mt ht nhn
50
p k z = m Ih
(3)
k z = m Ih
(4)
E = h
Eo
mI = s lng t spin t
Hz = 0
Hz
1
, v d : 1H,
2
13
C,
19
F,
31
P,
15
N s c hai
mI = +
1
v
2
mI =
1
2
kz
m = +
1
2
kz
m = -
1
2
m = +
1
2
Momen t ca ht nhn c I = 1 s c 3 v tr l :
mI = 1
kz
mI = 0
kz
mI = 1
kz
E
k
k
m = 0
m = -
1
2
Cc trng thi khc nhau trong t trng Hz s c mc nng lng khc nhau.
Nng lng tng tc E gia k vi t trng Hz l :
z
1
1
(5) E = m I hH z trng thi mI = c nng lng cao hn trng thi mI = + .
2
2
51
Khong cch gia hai trng thi nng lng lin nhau l :
E = m I hH z
(6)
trng cao tn xoay chiu c tn s cung cp nng lng ph hp vi phng trnh (6).
Trng hp ny s xut hin s cng hng gia trng xoay chiu v ht nhn.
Quy tc cng hng :
mI = 1
mc thp ln mc cao (hp th) v t cao xung thp (pht x) c cng xc sut. Nh c
s khc nhau nh v s chim ch trong mc nng lng thp hn m ta quan st c s
hp th trong th nghim cng hng.
S chim ch ca mt mc nng lng ca mt nhm ht nhn trong cn bng
N ''
= 1,000009 c
N
chiu m ta chiu vo. Do s chnh lch v s chim ch gia hai mc nng lng l qu
nh nn s nhanh chng b cn bng v tn hiu hp th s bin mt ("bo ho").
Mt khc, ht nhn cng cho mt nng lng trong khi cng hng thng qua trao
i nng lng vi mi trng xung quanh hoc gia cc ht nhn vi nhau mt cch
52
i vi 1H :
H0 = 104 G
53
HDD = 10
... 101 G
1
HA = 0 ... 10
HSS = 0 ... 10
vch rt rng.
II. C s thc nghim
C hai kh nng xc nh s hp th cng hng : Hoc gi t trng HO c
Ho = 23487 G
1
19
nhy tng i
11
13
14
31
N
20
40
60
80
100
54
S xung tn s radio, tip theo l thi gian thu nhn (FID) v khong cch ngt gia
hai xung (pulse delay)
55
NMR l:
HR = HR(B) HR(A) = H0(B A)
Khong cch ny ngoi s ph thuc vo hng s che chn A, B cn ph thuc vo
t trng ca thit b H0.
H R
Ngc li : B A =
=
H0
H R
H R(chun)
H R(chun) H R(mu)
H R(chun)
Khi tn s l c nh.
V HR c gi tr rt nh nn chuyn dch ho hc c t cho n v l ppm
6
56
Cht chun phi l nhng cht c nhng ht nhn b che chn nh nhau, tc l ch
cho mt tn hiu trong ph NMR. Cho 1H-NMR thng l TMS; ngi ta t cho TMS
= 0 ppm.
*) nh hng ca mt in t n : Vng ca i vi cc loi proton rt rng.
C ngha l v tr cng hng ca mt nhn proton nht nh s thay i theo loi v cu
trc trong phn cn li ca phn t. Nguyn nhn l s thay i mt in t ca proton
ta ang quan st bi tnh m in ca nguyn t bn cnh hoc nhm bn cnh.
V d : + Cc metyl halogenid:
Hp cht
Tnh m in ca halogen
chuyn dch ho hc
(ppm)
CH3J
3,0
2,15
CH3Br
3,2
2,65
CH3Cl
3,5
3,01
CH3F
4,0
4,22
+ OH, NH: tham gia to lin kt hiro che chn thay i, bin ng ln, ph
thuc vo loi lin kt, bn lin kt, nng , dung mi, nhit ...
V d : Trong MeOH tinh khit lin kt H mnh OH = 5,05, trong 1 M CH3OH
trong CCl4 OH = 3,7 ppm.
*) nh hng ca s bt ng hng (anisotropy) : Hiu ng che chn ln nht l t
cc nhm chc c in t .
V d nhn thm : T trng H0 gy ra t trng ngc chiu HA trong phn nhm,
c ng sc t trng ngc vi t trng H0. Vng ngoi vng thm th HA v H0 l
cng chiu. Nh vy l s che chn do nhn thm gy ra xung quanh n l bt ng
hng (anisotrop). Hiu qu l cc ht nhn nhng vng khc nhau c tn hiu b lch
khc nhau. Proton vng () s dch v trng H0 thp, proton vng (+) s dch v
trng H0 cao.
+ Do hiu ng anisotropy ca lin kt CC m : Ha hoc Ra b che chn mnh hn He
hoc Re.
57
chuyn dch ho hc ca proton nhm OH, SH, NH (, ppm, CCl4 hoc CDCl3).
58
Khng c
dng in vng
C dng
in vng
Hnh nn d hng
ca benzen
*) nh hng bi mt in t
CH
CH2
H
CH
12
CH
OH
11
10
H
H
H
CH3
H
H
H
H
H
H
CH3
H
H
H
(H ngoi) : -0,51
(vng) : 7,27; 6,95
(H ngoi) : 9,28
(trong) : -2,99
59
a
e
e
e
CH3
(e)
- CH3
(a)
e
a
system)
Trong ph NMR mi hng s tng tc phi c xc nh hai tn hiu, nu
60
[D2] Nc (D2O)
[D4] Axit axetic (CD3COOD)
[D1] Axit trifloroaxetic (F3CCOOD)
[D18] Axit hexametyl photpho triamit
(HMPT) [(CD3)2N)]3PO
Hp th ()
7,24
3,35
4,78
2,04
7,27
1,42
2,30
7,19
7,50
7,67
8,11
5,32
6,83
6,00
1,93
1,07
1,73
3,58
3,58
2,49
7,19
7,55
8,71
4,65
2,03
11,5
2,53
*
T
C th o nhit cao
nc (oC)
23
112 T
21
160 T
64,
98 T
T.si (oC)
77
46
215 H
- 30
61
64
95 T
6
7
95
56
80
81
111
211 H
97T
8
44
45
116T
108 T
40
150 H
146 H
82
35
66
12
19
42
102
189H
115
0
17
15
100
118
72
233H
61
13
C (tng tc
13
C H trong CHCl3)
Dng ph
V d : a) CH3CHO
b) CH3 O CH 2 CH 2 O CH3
c) CH3 CH 2 S CH3
HA
HB
Cl
NO 2
HA'
HB'
62
AX
> 6 cn cn iu kin
J AX
> 6 hay
>6
I ij
J
1
s vch = N + 1
2
H
H'
F
H''
H'
H''
H'''
1H
19F
I=1
S vch
( bi)
Cng tng i
1 (Singulet)
2 (Dublet)
1:1
3 (Triplet)
1:2:1
4 (Quartet)
1:3:3:1
5 (Quintet)
1:4:6:4:1
6 (Sextet)
1 : 5 : 10 : 10 : 5 : 1
7 (Septet)
1 : 6 : 15 : 20 : 15 : 6 : 1
1 (Singulet)
3 (Triplet)
1:1:1
5 (Quintet)
1:2:3:2:1
7 (Septet)
1:3:6:7:6:3:1
63
Cl
Cl
H"
H'
TMS
J
TMS
H'
1 : 2 : 1 (cng )
H''
T trng ph = 0 c xc sut gp hai.
Nh vy tn hiu ca H tch thnh 3 vch (triplet), trong vch gia c cng
gp i .
2.2. Tnh cht ca hng s tng tc J :
J khng ph thuc vo t trng ca thit b (H0)
64
J AX
> 6 th ta
c ph bc 1.
Trong ph NMR thng cc tn hiu b tch thnh nhiu vch, nguyn nhn l do
tng tc spin spin gia cc ht nhn.
2.4.1.1. Ph thuc vo gc nh din :
th Karplus
S ph thuc ny c Karplus chng minh bng l thuyt v khng nh qua
kinh nghim thc tin.
65
3. Cng tn hiu
Trong ph NMR cng tn hiu c xc nh bi s khc nhau v chim ch
mc nng lng gy ra bi phn b Boltzmann :
S ~ (N'' N')
ng tch phn
66
67
Gn tn hiu
68
69
70
6.2. Ph HMQC
6.3. Ph HMBC
71